JP4813918B2 - Toner, method for producing the same, and image forming method - Google Patents

Description

The present invention relates to a toner , a toner manufacturing method, and an image forming method.

  Conventionally, a method for developing an electrostatic charge image using toner is roughly classified into a method using a two-component developer in which a toner and a carrier are mixed, and a method using a one-component developer consisting only of a toner. is there.

  In the method using a two-component developer, the toner and the carrier are agitated to charge each of them with different polarities, and the electrostatic charge image having the opposite polarity is visualized by the charged toner. Specific examples include a magnet brush method using an iron powder carrier, a cascade method using a bead carrier, and a fur brush method.

  As a method using a one-component developer, a powder cloud method in which toner is sprayed, a contact development method in which toner is directly contacted with an electrostatic latent image for development, and a toner is slightly removed from the electrostatic latent image. Examples include a non-contact development method in which development is performed separately.

  As a toner applied to these developing methods, a toner in which a colorant such as carbon black or pigment is dispersed in a binder resin is used. In addition to these components, those containing a magnetic material such as magnetite are used as a magnetic toner.

  Thus, the toner used in various development methods is charged to a positive or negative charge according to the polarity of the electrostatic image to be developed. In order to charge the toner, the chargeability of the resin forming the toner can be used. However, since the chargeability is small, the obtained image is easily fogged and unclear. Accordingly, a dye, a pigment, or a charge control agent is added in order to impart desired chargeability to the toner.

  Examples of negative charge control agents include metal complexes of monoazo dyes, nitrohumic acid and its salts, salicylic acid, naphthoic acid, zinc dicarboxylic acid, metal complexes such as aluminum, cobalt, chromium and iron, sulfonated copper phthalocyanine pigments, etc. Is mentioned.

  However, the above-described dyes have a complicated structure and are not constant in properties, so that they are poor in stability, and many have a change in chargeability depending on the environment. Many of the metal complexes are colored, and when applied to a color toner, the color reproduction range of an image is narrowed. On the other hand, a compound containing a heavy metal has a safety problem although it has a large effect of improving the chargeability.

  Therefore, as a charge control agent that does not contain a metal, a phenol oligomer, calixarene (see Patent Documents 1 and 2), a compound having a bisphenol skeleton (see Patent Documents 3 to 5), and an aromatic fluorine compound (see Patent Document 6). Are known.

However, these charge control agents have a problem that, when a toner is produced using a wet granulation method, the charge control agent of the toner is liable to move to an aqueous phase or an interface with an aqueous phase. There is also a problem that the heat-resistant storage stability of the toner in the developing device is lowered.
Japanese Patent No. 3200459 JP-A-5-216277 Japanese Examined Patent Publication No. 4-16109 Japanese Patent Laid-Open No. 3-146964 Japanese Patent No. 3444113 Japanese Patent No. 2815613

SUMMARY OF THE INVENTION In view of the above-described problems of the prior art, the present invention provides a toner having good chargeability and excellent heat-resistant storage stability, a method for producing the toner, and an image forming method for forming an image using the toner. Objective.

According to the first aspect of the present invention, there is provided a toner having a chemical formula

で示される化合物を含有することを特徴とする。

It contains the compound shown by these, It is characterized by the above-mentioned.

According to the first aspect of the present invention, it is possible to provide a toner having good chargeability and excellent heat-resistant storage stability.

で示される化合物、結着樹脂及び着色剤を含有する材料を有機溶媒に溶解又は分散させて第一の液を調製する工程と、該第一の液を水性溶媒中で分散させる工程を有することを特徴とする。 According to a second aspect of the present invention, in the toner production method, the chemical formula

A step of preparing a first liquid by dissolving or dispersing a material containing a compound represented by the above, a binder resin, and a colorant in an organic solvent; and a step of dispersing the first liquid in an aqueous solvent. It is characterized by.

According to the invention described in claim 2, a good band conductivity, it is possible to obtain a toner having excellent heat storage stability.

で示される化合物を含有する材料をモノマーに溶解又は分散させて第一の液を調製する工程と、該第一の液を水性溶媒中で乳化させて第二の液を調製する工程と、該第二の液に含まれる前記モノマーを重合して分散体を作製する工程と、該分散体を着色剤の分散体を含有する分散体と凝集させて、融着させる工程を有することを特徴とする。 According to a third aspect of the present invention, in the toner production method, the chemical formula

A step of preparing a first liquid by dissolving or dispersing a material containing a compound represented by formula (1) in a monomer; a step of emulsifying the first liquid in an aqueous solvent; A step of polymerizing the monomer contained in the second liquid to prepare a dispersion, and a step of aggregating the dispersion with a dispersion containing a dispersion of a colorant and fusing the dispersion. To do.

According to the invention described in claim 3, a good band conductivity, it is possible to obtain a toner having excellent heat storage stability.

で示される化合物、結着樹脂及び着色剤を含有する材料を水性溶媒中で分散させて分散体を作製する工程と、該分散体を凝集させて、融着させる工程を有することを特徴とする。 According to a fourth aspect of the present invention, in the toner production method, the chemical formula

A material containing a compound represented by the above, a binder resin and a colorant is dispersed in an aqueous solvent to produce a dispersion, and the dispersion is agglomerated and fused. .

According to the invention described in claim 4, a good band conductivity, it is possible to obtain a toner having excellent heat storage stability.

で示される化合物及び着色剤を含有する材料をモノマーに溶解又は分散させて第一の液を調製する工程と、該第一の液を水性溶媒中で分散させて第二の液を調製する工程と、該第二の液に含まれる前記モノマーを重合する工程を有することを特徴とする。 According to a fifth aspect of the present invention, in the toner production method, the chemical formula

A step of preparing a first liquid by dissolving or dispersing a material containing a compound and a colorant represented by formula (1) in a monomer, and a step of preparing a second liquid by dispersing the first liquid in an aqueous solvent. And a step of polymerizing the monomer contained in the second liquid.

According to the invention of claim 5, a good band conductivity, it is possible to obtain a toner having excellent heat storage stability.

According to a sixth aspect of the present invention, in the image forming method, an image is formed using the toner according to the first aspect.

According to the invention described in claim 6, it is possible to provide an image forming method capable of forming a high quality image.

According to the present invention, it is possible to provide a toner having good chargeability and excellent heat-resistant storage stability, a method for producing the toner, and an image forming method for forming an image using the toner.

  Next, the best mode for carrying out the present invention will be described with reference to the drawings.

  The bisphenol compound used in the present invention has a general formula

で示される。ここで、Ｘ_１、Ｘ_２、Ｘ_３及びＸ_４は、それぞれ独立に水素原子又はハロゲン原子であり、水素原子が好ましい。また、Ｙは、炭素数が３以上である二価連結基であり、炭素数が３以上３０以下である二価連結基が好ましく、炭素数が４以上２０以下であるアルキレン基がさらに好ましい。二価連結基の炭素数が大きすぎると、トナーの帯電性又はトナーへの均一分散性が低下する。

Indicated by Here, X ₁ , X ₂ , X ₃ and X ₄ are each independently a hydrogen atom or a halogen atom, preferably a hydrogen atom. Y is a divalent linking group having 3 or more carbon atoms, preferably a divalent linking group having 3 to 30 carbon atoms, and more preferably an alkylene group having 4 to 20 carbon atoms. When the carbon number of the divalent linking group is too large, the chargeability of the toner or the uniform dispersibility in the toner is lowered.

  In the present invention, when the bisphenol compound has a cyclic structure, the affinity for the binder resin is improved as a nonpolar group having an appropriate degree of freedom in the cyclic structure. Thereby, in a wet granulation method, transfer to an aqueous solvent and uneven distribution can be suppressed. For example, in the case of using a compound having two alkyl groups instead of Y, if the chain length of the alkyl group is short like bisphenol A, the affinity with the binder resin is poor. Transition and uneven distribution of the surface occur, leading to deterioration of the image due to a decrease in chargeability and a decrease in durability. On the other hand, if the chain length of the alkyl group is long, such a phenomenon is suppressed, but since the binder resin is plasticized, the heat resistant storage stability is lowered.

  The bisphenol compound used in the present invention includes a chemical structural formula

で示される化合物が挙げられる。これらの化合物は、いずれも白色又はほぼ白色である。

The compound shown by these is mentioned. These compounds are all white or almost white.

  The bisphenol compound used in the present invention can be synthesized using a known method in which phenols and cyclic ketones are reacted in the presence of an acidic catalyst. The phenol is not particularly limited as long as it is a monovalent aromatic hydroxy compound that forms a bisphenol compound by condensation with cyclic ketones. Specific examples of phenols include phenol, o-cresol, m-cresol, o-chlorophenol, m-chlorophenol, o-ethylphenol, m-ethylphenol, 2,5-xylenol, 3,5-xylenol, 2,6-xylenol, 2,5-di-t-butylphenol, 2,6-di-t-butylphenol, o-phenylphenol and the like can be mentioned. On the other hand, cyclic ketones are not particularly limited as long as they are condensed with phenols to form bisphenol compounds. Specific examples of cyclic ketones include cyclopentanone, cyclohexanone, cyclononanone, cyclooctanone, cyclododecanone, 2-norbornanone, 2-adamantanone, 1-indanone, 2-indanone, α-tetralone, β-tetralone, Examples include fluorenone and derivatives thereof.

  In the condensation reaction of phenols and cyclic ketones, an excess amount of phenols is usually charged with respect to the cyclic ketones. Excess phenols can be recovered after the reaction and reused. An acid catalyst and a cocatalyst can be used for the condensation reaction. As the acid catalyst, known ones such as hydrogen chloride, sulfuric acid, trimethylsilyl chloride, sulfonic acids, and cation exchange resins that are generally used in the production of bisphenols can be used. Moreover, as a co-catalyst, well-known things, such as an alkyl mercaptan, an alkyl dimercaptan, a mercaptopropionic acid, can be used.

  Further, as disclosed in JP-A-10-212433, a strongly acidic sulfonic acid type ion exchange resin modified with a substituent having a function as a promoter such as a mercapto group is used instead of an acid catalyst and a promoter. Bisphenol compounds can also be synthesized.

  In the present invention, the addition amount of the bisphenol compound is appropriately determined depending on the type of the binder resin, the presence or absence of additives added as necessary, and the toner production method including the dispersion method. It is preferably 1 to 20% by weight. When the addition amount is less than 0.1% by weight, the chargeability of the toner is lowered, which is not practical. On the other hand, when the addition amount exceeds 20% by weight, the chargeability of the toner becomes too large and the electrostatic attraction with the carrier increases, so that the fluidity of the developer decreases and the image density decreases. To do.

  The toner of the present invention may contain a known charge control agent in addition to the bisphenol compound.

  Known charge control agents include metal complex salts of monoazo dyes, nitrohumic acid and its salts, zinc, salicylic acid, naphthoic acid and dicarboxylic acid metal complexes such as aluminum, cobalt, chromium and iron, sulfonated copper phthalocyanine pigments , Nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts including fluorine-modified quaternary ammonium salts, alkylamides, phosphorus A simple substance or a compound thereof, a simple substance of tungsten or a compound thereof, a fluorine-based surfactant, or the like can be used. Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E- of salicylic acid metal complex 84, phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt Copy charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (above, Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinaclide And azo pigments. In addition, a polymer having a sulfonic acid group, a carboxyl group, a quaternary ammonium salt or the like in the side chain can be used.

  The toner of the present invention preferably contains a binder resin, a colorant, wax and the like.

  The binder resin is not particularly limited as long as it is generally used as a resin for toner, and examples thereof include polyester resins, polyurethane resins, polyurea resins, epoxy resins, vinyl resins, and copolymers thereof. Of these, polyester resins, vinyl resins, and block copolymers and graft copolymers thereof are preferable.

  As the colorant, known dyes and pigments can be used, such as carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa Yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead. , Titanium yellow, Polyazo yellow, Oil yellow, Hansa yellow (GR, A, RN, R), Pigment yellow L, Benzidine yellow (G, GR), Permanent yellow (NCG), Vulcan fast yellow (5G, R), Tartrazine lake, quinoline yellow lake, anthrazan yellow BGL, isoindolinone yellow, bengara, red lead, lead vermilion, cadmium red, cadmium mercurial red, antimon vermilion, permanent red 4R, para red, phise red, p-chloro- o-Nitroaniline , Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Velcan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, polyazo Chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyaning Examples include lean, anthraquinone green, titanium oxide, zinc white, litbon, and mixtures thereof. The content of the colorant in the toner is usually 1 to 15% by weight, and preferably 3 to 10% by weight.

  As the wax, known ones can be used, such as polyethylene, polypropylene, ethylene-propylene copolymer, Fischer-Tropsch wax, higher fatty acid, higher alcohol, higher fatty acid amide, higher fatty acid ester of higher alcohol, higher fatty acid of ethylene glycol. Synthetic wax such as diester, higher fatty acid triester of glycerin, higher fatty acid tetraester of pentaerythritol, higher fatty acid hexaester of dipentaerythritol, paraffin wax, microcrystalline wax, rice wax, carnauba wax, lanolin wax, candelilla wax, etc. Natural wax and the like.

  The method for producing the toner of the present invention is not particularly limited, and examples thereof include known wet granulation methods such as a dissolution suspension method, a suspension polymerization method, and an emulsion aggregation method, and a pulverization method. In particular, the toner manufactured using the wet granulation method can control the chargeability because the transfer of the charge control agent to the aqueous solvent and the uneven distribution on the toner surface are suppressed.

  As a method for producing toner using the dissolution suspension method, at least a solution or dispersion obtained by dissolving or dispersing a toner composition comprising a binder resin, a colorant and a bisphenol compound in an organic solvent is used. In an aqueous solvent in which inorganic dispersants or resin fine particles are present, use a normal stirrer, homomixer, homogenizer, etc. to disperse the toner with the desired particle size distribution, and then remove the organic solvent. There is a method of obtaining a toner slurry by doing so. The toner can be isolated by washing and filtration according to a known method and drying.

  An organic solvent having a boiling point of less than 100 ° C. is preferably used because it can be easily removed. Such organic solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate. , Methyl ethyl ketone, methyl isobutyl ketone and the like, and may be used alone or in combination of two or more.

  The aqueous solvent may be water alone, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohols such as methanol, isopropanol and ethylene glycol, cellosolves such as dimethylformamide, tetrahydrofuran and methyl cellosolve, and lower ketones such as acetone and methyl ethyl ketone. The amount of the aqueous solvent used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts by weight of the toner material. When the amount of the aqueous solvent used is less than 50 parts by weight, the dispersion state of the toner material is deteriorated. Moreover, when it exceeds 2000 weight part, it is not economical.

  Inorganic dispersants include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, Alumina, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite, or the like can be used.

  The resin forming the resin fine particles is not particularly limited as long as it is a resin that can form an aqueous dispersion, but vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, Examples thereof include phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like. These resins may be either thermoplastic resins or thermosetting resins, and two or more of these resins may be used in combination. Among these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained.

  Further, as a toner composition, a prepolymer such as polyester may be added, and a polyaddition reaction may be carried out in the process of producing the toner.

  As a method for producing a toner using an emulsion aggregation method, at least a bisphenol compound dissolved or dispersed in a monomer is emulsified in an aqueous solvent using an emulsifier and polymerized using a polymerization initiator. A method of obtaining a toner slurry by aggregating and fusing the obtained resin dispersion containing a bisphenol compound with a dispersion of a colorant, a wax dispersion, etc., and preparing a dispersion of the bisphenol compound to obtain a resin dispersion And a method of obtaining a toner slurry by agglomeration and fusion with a dispersion of a colorant, a dispersion of wax, and the like. The toner can be isolated by washing and filtration according to a known method and drying.

  As the monomer, a vinyl monomer can be used. Styrene such as styrene, p-methylstyrene, p-styrenesulfonic acid, p-chlorostyrene, p-carboxystyrene, α-methylstyrene, divinylbenzene, and derivatives thereof, Vinyl esters such as vinyl naphthalene, vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, (meth) acrylic acid, methyl (meth) acrylate, (meth) acrylic Ethyl acetate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, decyl (meth) acrylate, (meth ) Dodecyl acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 1,6-hexanediol diacrylate, 1,10-decandiol diacrylate, etc. (meth) acrylic acid and its esters, N, N -(Meth) acrylamide such as dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, maleic acid, maleic anhydride, maleic acid monoester, maleic acid diester, itacon Examples include acids and esters thereof, and various vinyl esters.

  As the emulsifier, known ones can be used, and anionic properties such as sodium alkyl sulfate, sodium alkylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium alkyl naphthalene sulfonate, sodium dialkyl sulfosuccinate, sodium alkyl diphenyl ether disulfonate, etc. Nonionic emulsifiers such as emulsifiers, polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxypropyl alkyl ethers, sorbitan fatty acid esters, cationic emulsifiers such as alkyltrimethylammonium chloride and dialkyldimethylammonium chloride, amphoteric emulsifiers such as alkylbetaine Etc. Among these, an anionic emulsifier is preferable because it is excellent in emulsion stability. Further, by using a reactive emulsifier having both a hydrophilic group and a polymerizable functional group, the dispersion state of the polymerized dispersion can be stabilized.

  As the polymerization initiator, known ones can be used. Ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, 4,4′-azobis (4-cyanovaleric acid) and salts thereof, 2,2 Water-soluble polymerization initiators such as' -azobis (2-amidinopropane) salt, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile), 1, Azo or diazo polymerization initiators such as 1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), azobis (isobutyronitrile) Benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide Sid, polymerization initiators such as oil-soluble, such as lauroyl peroxide and the like.

  As a method for producing a toner using the suspension polymerization method, a colorant, a bisphenol compound, a polymerization initiator, and other additives are added to the monomer, and the toner is uniformly dissolved or dispersed using a homogenizer, an ultrasonic disperser, or the like. A method may be mentioned in which the dissolved solution or dispersion is dispersed in an aqueous solvent containing a dispersion stabilizer using a normal stirrer, homomixer, homogenizer or the like, and polymerized. It is preferable to perform granulation by adjusting the stirring speed and time so that the monomer droplets have a desired toner particle size. Thereafter, the particle state is maintained by the action of the dispersion stabilizer, and stirring may be performed so that the particles do not settle. The polymerization temperature is usually 40 ° C. or higher, preferably 50 to 90 ° C. Further, the temperature may be raised in the latter half of the polymerization reaction. Furthermore, in order to remove unreacted monomers, by-products and the like that cause odor when fixing the toner, the aqueous solvent may be distilled off in the latter half or after the completion of the polymerization reaction. After completion of the polymerization reaction, the produced toner is recovered by washing and filtration and dried.

  As a dispersion stabilizer, as an inorganic compound, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, sulfuric acid Examples include calcium, barium sulfate, bentonite, silica, and alumina. Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, polyacrylic acid and its salt, starch and the like. These can be used by dispersing in an aqueous solvent. In addition, it is preferable that a dispersion stabilizer adds 0.2 to 20 weight% with respect to a monomer. When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, but in order to obtain fine particles, fine particles of the inorganic compound may be generated in a dispersion medium. For example, in the case of tricalcium phosphate, an aqueous sodium phosphate solution and an aqueous calcium chloride solution may be mixed under high-speed stirring.

  As a method for producing a toner using a pulverization method, at least a step of mechanically mixing a toner composition comprising a binder resin, a bisphenol compound and a colorant, and a step of melt-kneading according to conventionally known means, Examples thereof include a toner production method having a pulverizing step and a classification step. In addition, in the mechanical mixing step or the melt-kneading step, a toner other than the toner that becomes the product obtained in the pulverization or classification step may be reused.

  The mechanical mixing step may be performed under normal conditions using a mixer having a stirring blade, and is not particularly limited. When this step is completed, the mixture is charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. Specifically, a KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), a TEM type extruder (manufactured by Toshiba Machine Co., Ltd.), a twin screw extruder (manufactured by Kay C.K.), and a PCM type twin screw extruder. (Ikegai Iron Works Co., Ltd.), Conyder (Bus Co., Ltd.) and the like. The melt-kneading needs to be performed under conditions that do not break the molecular chain of the binder resin. If the melt kneading temperature is too lower than the softening point of the binder resin, the molecular chain will be broken, and if it is too high, the dispersion of the bisphenol compound, colorant, etc. will not proceed, so the melt kneading temperature will depend on the softening point of the resin. Is preferably set appropriately.

  When the step of melt kneading is completed, the kneaded product is pulverized. In the pulverizing step, it is preferable to pulverize after coarse pulverization. Examples of such pulverization methods include a method of pulverizing by colliding with a collision plate in a jet stream, a method of pulverizing particles by colliding with each other in a jet stream, and pulverizing with a narrow gap between a mechanically rotating rotor and a stator. A method is mentioned. After this step is completed, the pulverized product is classified in an air stream using centrifugal force or the like, whereby a toner having a predetermined particle diameter can be obtained.

  The image forming method of the present invention forms an image using the toner of the present invention. The toner of the present invention may be used as a one-component developer, or may be mixed with a carrier and used as a two-component developer.

  FIG. 1 shows an example of an image forming apparatus that forms an image using a one-component developer. In this image forming apparatus, a photosensitive member (photosensitive belt 102) which is a latent image holding unit, and toners of four different colors of yellow, magenta, cyan and black are filled on the right side of the photosensitive belt 102 in the drawing. Developing devices 1Y, 1M, 1C, and 1K are disposed. An exposure device 104 for forming a latent image on the photosensitive belt 102 is disposed below the developing device 1C, and a lower portion of the photosensitive belt 102 is disposed. A charging device 105 is disposed. A paper feed cassette 106 that stores a recording medium 106 a is disposed below the exposure device 104. An intermediate transfer member (transfer drum 107) is disposed on the left side of the photosensitive belt 102 in the drawing, and a fixing device 101 is disposed thereon. Further, the developing devices 1Y, 1M, 1C, and 1K have an identification shape portion (not shown).

  The photosensitive belt 102 is driven in the direction of the arrow 102a. The photosensitive layer on the surface of the driven photosensitive belt 102 is uniformly charged by the charging device 105. Next, image or character information from a personal computer, an image scanner or the like is exposed in dot units using the exposure device 104 to form an electrostatic latent image on the photosensitive belt 102. The electrostatic latent image formed on the photosensitive belt 102 is developed into a corresponding color toner image by any of the developing devices 1Y, 1M, 1C, and 1K. The toner image formed on the photosensitive belt 102 is transferred onto the transfer drum 107 that rotates in the direction of the arrow 107a.

  By sequentially performing the above-described cycle for the developing devices 1Y, 1M, 1C, and 1K, a color toner image in which toners of four colors are superimposed is formed on the transfer drum 107. Accordingly, a recording medium 106a such as paper or OHP is sent from the paper feed cassette 106 at the appropriate timing, whereby the toner image is transferred onto the recording medium. The recording medium on which the toner image has been transferred passes through the fixing device 101, and heat and pressure are applied, whereby the toner is melted, fixed on the recording medium, and discharged to the top of the image forming apparatus.

  Next, the developing device will be described. FIG. 2 shows a schematic diagram of the developing devices 1Y, 1M, 1C, and 1K. The toner storage chamber 1 stores toner 2 used for development. A conveying blade 3 is disposed in the toner storage chamber 1, and is configured to convey the toner 2 to the developing roll 5 side by rotation thereof. A supply roll 4 made of a conductive elastic foam roll is disposed at the front of the toner storage chamber 1, and the toner 2 conveyed to the front of the toner storage chamber 1 is supplied to the developing roll 5. The toner 2 supplied onto the developing roll 5 is regulated to a toner layer thickness appropriate for development by the regulating blade 6, and the toner is frictionally charged by sliding with the regulating blade 6.

The following will explain the present invention therefore to an embodiment, the present invention is not limited to these examples. In addition, the part used in the Example means a weight part.
(Reference Example 1)
In a reaction vessel equipped with a stirrer and a thermometer, water 683 parts, ethylene salt methacrylate adduct sulfate sodium salt Eleminol RS-30 (manufactured by Sanyo Chemical Industries), 83 parts styrene, 83 parts methacrylic acid, acrylic acid When 83 parts of butyl and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. Next, the temperature was raised to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to obtain a resin fine particle dispersion. It was 38 nm when the volume average particle diameter of the resin fine particle dispersion was measured using UPA-150 (manufactured by JGC Corporation). When a part of the resin fine particle dispersion was dried and isolated, the glass transition temperature of the resin was 56 ° C. After mixing for 10 minutes, the operation of filtering was performed twice.

  990 parts of water, 80 parts of a resin fine particle dispersion, 40 parts of 48.5% aqueous solution of derminol MON-7 (manufactured by Sanyo Chemical Industries) of sodium dodecyl diphenyl ether disulfonate, and 90 parts of ethyl acetate are mixed and stirred to obtain a milky white dispersion medium. It was.

  In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 220 parts of bisphenol A ethylene oxide 2-mole adduct, 561 parts of bisphenol A propylene oxide 3-mole adduct, 218 parts of terephthalic acid, 48 parts of adipic acid and dibutyltin oxide 2 parts were charged, reacted for 8 hours at 230 ° C. under normal pressure, and further allowed to react for 5 hours under reduced pressure of 10-15 mmHg. Then, 45 parts of trimellitic anhydride was added to the reaction vessel, and 2 parts at 180 ° C. under normal pressure. The reaction was carried out for a time to obtain a low molecular weight polyester. The low molecular weight polyester had a number average molecular weight of 2500, a weight average molecular weight of 6700, a glass transition temperature of 43 ° C., and an acid value of 25 mgKOH / g.

  In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted under reduced pressure of 10 to 15 mmHg for 5 hours to obtain an intermediate polyester. The intermediate polyester had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition temperature of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 49 mgKOH / g.

  Next, 411 parts of intermediate polyester, 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours to obtain a prepolymer. It was. The free isocyanate% of the prepolymer was 1.53% by weight.

  40 parts of Legal 400R (manufactured by Cabot Corp.) as carbon black, polyester resin RS-801 (manufactured by Sanyo Chemical Co., Ltd.) having an acid value of 10 mgKOH / g, a weight average molecular weight of 20000, and a glass transition temperature of 64 ° C. 60 parts and 30 parts of water were mixed using a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes using two rolls set at a surface temperature of 130 ° C., and pulverized with a pulverizer to a particle size of 1 mm to obtain a master batch.

  Chemical structural formula of 378 parts low molecular weight polyester, 110 parts carnauba wax, 105 parts in a container equipped with a stir bar and thermometer

で示されるビスフェノール化合物１及び酢酸エチル９４７部を仕込み、撹拌しながら８０℃に昇温し、８０℃で５時間保持した後、１時間で３０℃に冷却した。次に、マスターバッチ５００部、酢酸エチル５００部を容器に加え、１時間混合し、トナー組成物混合液を得た。

Were added, and the mixture was heated to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts of a master batch and 500 parts of ethyl acetate were added to the container and mixed for 1 hour to obtain a toner composition mixture.

  1324 parts of the toner composition mixed solution was transferred to a container, and using an ultra visco mill (manufactured by Imex Co.) as a bead mill, the liquid feeding speed was 1 kg / hour, the peripheral speed of the disk was 6 m / second, and the diameter was 0.5 mm. 80% by volume of the zirconia beads were filled, and the pigment and the wax were dispersed under the condition of 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of low molecular weight polyester was added, and one pass was performed with a bead mill under the above conditions to obtain a pigment / wax dispersion. The solid content concentration of the pigment / wax dispersion was 50%. The solid content concentration was measured by drying at 130 ° C. for 30 minutes.

  648 parts of pigment / wax dispersion, 154 parts of prepolymer and 4 parts of isophoronediamine are charged into a container and mixed for 1 minute at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.), followed by 1200 parts of dispersion medium in the container. Was added and mixed for 20 minutes at 13000 rpm using a TK homomixer to obtain an emulsified slurry.

  The emulsified slurry was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain a dispersed slurry.

  After filtering 100 parts of the dispersion slurry under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, followed by mixing at 12000 rpm for 10 minutes using a TK homomixer, followed by filtration. The filter cake was added with 100 parts of a 10% aqueous sodium hydroxide solution, subjected to ultrasonic vibration, mixed at 12000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure twice. 100 parts of 10% hydrochloric acid was added to the filter cake, and the mixture was mixed for 10 minutes at 12000 rpm using a TK homomixer, followed by filtration. After adding 300 parts of ion-exchanged water to the filter cake, mixing for 10 minutes at 12000 rpm using a TK homomixer, the operation of filtering was performed twice.

Using a circulating dryer, the filter cake was dried at 45 ° C. for 48 hours and sieved with a mesh having an opening of 75 μm to obtain toner mother particles. The volume average particle diameter was 5.9 μm, the number average particle diameter was 5.2 μm, and the average circularity was 0.971. Next, 100 parts of toner base particles, 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide were mixed using a Henschel mixer to obtain a toner.
( Reference Example 2)
As a cyan pigment, 50 parts of C.I. I. Pigment Blue 15: 3, 10 parts of sodium dodecyl sulfate and 200 parts of ion-exchanged water were dispersed using a sand grinder mill to obtain a colorant dispersion having a volume average particle diameter of 170 nm.

  A 5000 ml separable flask equipped with a stirrer, temperature sensor, cooling tube, and nitrogen introducing device was charged with a solution prepared by dissolving 4.05 parts of sodium dodecyl sulfate in 2500 parts of ion-exchanged water and stirred at 230 rpm under a nitrogen stream. The temperature was raised to 80 ° C. while stirring at a speed. Next, after adding a solution prepared by dissolving 9.62 parts of potassium persulfate in 200 parts of ion-exchanged water, 568 parts of styrene, 164 parts of n-butyl acrylate, 68 parts of methacrylic acid, and 16.51 of n-octyl mercaptan. Part of the mixture was added dropwise over 1.5 hours, and the mixture was heated and stirred at 80 ° C. for 2 hours to carry out polymerization (first stage polymerization) to prepare latex (1H). The weight average particle diameter of the latex (1H) was 68 nm.

In a flask equipped with a stirrer, 123.81 parts of styrene, 39.51 parts of n-butyl acrylate, 12.29 parts of methacrylic acid, 0.72 parts of n-octyl mercaptan, chemical structural formula C (CH ₂ OCO ( CH ₂ ) ₂₀ CH ₃ ) ₄
A monomer solution was prepared by charging 75 parts of an ester wax represented by the formula (10) and 10 parts of the bisphenol compound 1, heating to 80 ° C. and dissolving.

Chemical structural formula C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₂ OSO ₃ ⁻ Na ⁺
A solution prepared by dissolving 0.6 part of the surfactant shown in 2700 parts of ion-exchanged water is heated to 98 ° C., 32 parts of latex (1H) in terms of solid content is added, and then the monomer solution is added to circulate. A dispersion was prepared by mixing and dispersing for 8 hours using a mechanical disperser Claremix (M Technique Co., Ltd.) having a route.

  Next, a solution obtained by dissolving 6.12 parts of potassium persulfate in 250 parts of ion-exchanged water is added to this dispersion, and the mixture is heated and stirred at 82 ° C. for 12 hours, whereby polymerization (second stage polymerization) is performed. To obtain latex (1HM).

  After adding a solution prepared by dissolving 8.8 parts of potassium persulfate in 350 parts of ion exchange water to latex (1HM), at 82 ° C., 350 parts of styrene, 95 parts of n-butyl acrylate, 5 parts of methacrylic acid, and A 1 mol% n-octyl mercaptan mixture of monomers was added dropwise over 1 hour. After completion of the dropping, the mixture was heated and stirred at 82 ° C. for 2 hours to carry out polymerization (third stage polymerization) and cooled to 28 ° C. to obtain latex (1HML).

  In a reaction vessel (four-necked flask) equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device, 420 parts of latex (1HML) (solid content conversion), 900 parts of ion-exchanged water and 150 parts of a colorant dispersion are added. Charged and stirred. After adjusting the temperature in a container to 30 degreeC, 5N sodium hydroxide aqueous solution was added and pH was adjusted to 8-10.

  Next, a solution prepared by dissolving 65 parts of magnesium chloride hexahydrate in 1000 parts of ion-exchanged water was added over 10 minutes with stirring. After standing for 3 minutes, the temperature was raised to 92 ° C. to produce aggregated particles. In this state, the particle diameter of the aggregated particles was measured using a Coulter Counter TA-II (manufactured by Beckman Coulter). When the number average particle diameter reached 6.1 μm, 80.4 parts of sodium chloride was added. Particle growth was stopped by adding a solution dissolved in 1000 parts of ion-exchanged water. Furthermore, as a ripening treatment, the particles were fused and the phase separation of the crystalline substance was continued by heating and stirring at 94 ° C. In this state, the shape of the fused particles was measured using FPIA-2000 (manufactured by Sysmex Corporation), and when the average circularity reached 0.960, the mixture was cooled to 30 ° C. and stirring was stopped. The produced fused particles were filtered, washed repeatedly with ion exchange water at 45 ° C., and dried with hot air at 40 ° C. to obtain toner mother particles. The number average particle size and shape factor of the toner base particles were measured again and found to be 6.0 μm and 0.962, respectively.

To 100 parts of toner base particles, 0.5 part of hydrophobic silica H2000 (manufactured by Wacker Soot), 0.5 part of hydrophobic silica (HMDS-treated product) having a primary particle diameter of 21 nm, titanium oxide STT-30S (manufactured by Titanium Kogyo) ) 0.5 part and 1 part of strontium titanate having an average particle diameter of 0.2 μm were added, mixed using a 9 L Henschel mixer for 5 minutes at a peripheral speed of 40 m / second, and then sieved with a sieve having an aperture of 106 μm. A toner was obtained. The shape and particle size of the toner did not change with the addition of hydrophobic silica and hydrophobic titanium oxide.
( Reference Example 3)
In a four-necked vessel, 360 parts of ion-exchanged water and 430 parts of a 0.1 M aqueous sodium phosphate solution were charged and kept at 60 ° C. while stirring at 15000 rpm using a high-speed stirrer homomixer. To this, 34 parts of 1M calcium chloride aqueous solution was gradually added to prepare an aqueous dispersion containing calcium phosphate which is a fine hardly water-soluble dispersion stabilizer.

  On the other hand, as dispersoids, 83 parts of styrene, 17 parts of n-butyl acrylate, 5 parts of copper phthalocyanine pigment, 0.8 part of bisphenol compound 1, 0.05 part of divinylbenzene, 5 parts of ester wax having a melting point of 75 ° C, After 2 parts of a hydrocarbon wax and 5 parts of a polyester resin having a weight average molecular weight of 25000 and an acid value of 15 mg KOH / g were dispersed using an attritor (manufactured by Mitsui Kinzoku Co., Ltd.) for 3 hours, 2,2′- 3 parts of azobis (2,4-dimethylvaleronitrile) was added to prepare a monomer composition.

  Next, the monomer composition was charged into the aqueous dispersion, and the monomer composition was granulated in a nitrogen atmosphere at 60 ° C. while stirring at a high speed stirring device at 15000 rpm for 4 minutes. Thereafter, the stirring device was changed to one equipped with paddle stirring blades, and the polymerization was carried out for 5 hours while maintaining at 60 ° C. while stirring at 200 rpm.

  Then, it heated up at 80 degreeC and superposition | polymerization was performed. After cooling, dilute hydrochloric acid was added to adjust the pH to 1.2 to dissolve calcium phosphate. Further, after solid-liquid separation by pressure filtration, washing was performed with 18000 parts of water. Then, it was dried using a vacuum drying device to obtain toner base particles having a weight average particle diameter of 7.1 μm.

Next, 100 parts of toner base particles are each added dryly with titanium oxide having a hydrophobized average particle size of 30 nm and hydrophobized silica fine particles having a specific surface area of 120 m ² / g, respectively. A toner was obtained.
( Reference Example 4)
100 parts of a polyester resin having a weight average molecular weight of 27,000 and an acid value of 18 mg KOH / g, 5 parts of polyethylene wax having a melting point of 120 ° C., 5 parts of C.I. I. Pigment Blue 15: 3 and 1.5 parts of bisphenol compound 1 were stirred and mixed using a Henschel mixer, kneaded using a biaxial extruder, and after cooling, the volume average particle diameter was 9 ± 0.5 μm. The toner base particles were obtained by pulverization and classification as described above. Regarding the kneading conditions, the temperature of the kneader was set so that the temperature of the kneaded product at the kneader outlet was about 130 ° C.

To the obtained toner base particles, 0.5% by weight of hydrophobic silica and 0.3% by weight of titanium oxide were added and mixed to obtain a toner.
(Example 5)
Chemical structural formula instead of bisphenol compound 1

で示されるビスフェノール化合物２を用いた以外は、参考例１と同様にトナーを作製した。
（参考例６）
ビスフェノール化合物１の代わりに、化学構造式

A toner was prepared in the same manner as in Reference Example 1 except that the bisphenol compound 2 shown in FIG.
( Reference Example 6)
Chemical structural formula instead of bisphenol compound 1

で示されるビスフェノール化合物３を用いた以外は、参考例１と同様にトナーを作製した。
（参考例７）
ビスフェノール化合物１の代わりに、化学構造式

A toner was prepared in the same manner as in Reference Example 1 except that the bisphenol compound 3 shown in FIG.
( Reference Example 7)
Chemical structural formula instead of bisphenol compound 1

で示されるビスフェノール化合物４を用いた以外は、参考例１と同様にトナーを作製した。
（参考例８）
反応槽に、イオン交換水３５部を投入し、非イオン性界面活性剤ノニポール４００（三洋化成社製）０．４３部及びアニオン性界面活性剤ネオゲンＲ（ドデシルベンゼンスルホン酸ナトリウム）（第一工業製薬社製）０．５９部を溶解させた。次に、スチレン２５部、アクリル酸ｎ−ブチル３部、アクリル酸０．５６部、ドデカンチオール１．１部及び四臭化炭素０．３部を予め混合溶解させたモノマー溶液を反応槽に分散させて乳化し、１０分間ゆっくりと混合しながら、さらにイオン交換水７部に過硫酸アンモニウム０．２９部を溶解させた溶液を投入し、窒素置換を行うことにより乳化液を得た。その後、さらに攪拌しながら、乳化液の温度が７０℃になるまで加熱し、この状態で６時間そのまま乳化重合を継続することにより、樹脂微粒子の体積平均粒子径が２１０ｎｍ、ガラス転移温度が５７℃、重量平均分子量が１６５００のアニオン性の樹脂微粒子分散液１を得た。

A toner was prepared in the same manner as in Reference Example 1 except that the bisphenol compound 4 shown in FIG.
(Reference Example 8)
35 parts of ion-exchanged water is put into the reaction tank, 0.43 part of nonionic surfactant Nonipol 400 (manufactured by Sanyo Chemical Co., Ltd.) and anionic surfactant Neogen R (sodium dodecylbenzenesulfonate) (Daiichi Kogyo) 0.59 part (manufactured by Pharmaceutical Co., Ltd.) was dissolved. Next, a monomer solution in which 25 parts of styrene, 3 parts of n-butyl acrylate, 0.56 parts of acrylic acid, 1.1 parts of dodecanethiol and 0.3 parts of carbon tetrabromide were mixed and dissolved in advance was dispersed in the reaction vessel. The mixture was emulsified and slowly mixed for 10 minutes, and then a solution in which 0.29 part of ammonium persulfate was dissolved in 7 parts of ion-exchanged water was added to perform nitrogen substitution to obtain an emulsion. Thereafter, while further stirring, the emulsion is heated until the temperature of the emulsion reaches 70 ° C., and in this state, the emulsion polymerization is continued for 6 hours, whereby the volume average particle diameter of the resin fine particles is 210 nm and the glass transition temperature is 57 ° C. An anionic resin fine particle dispersion 1 having a weight average molecular weight of 16,500 was obtained.

  35 parts of ion-exchanged water was added to the reaction vessel, 0.43 part of nonionic surfactant Nonipol 400 (manufactured by Sanyo Kasei Co., Ltd.) and anionic surfactant Neogen R (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.9 Part was dissolved. Next, a monomer solution in which 19.4 parts of styrene, 8.3 parts of n-butyl acrylate and 0.57 parts of acrylic acid are mixed and dissolved in advance is dispersed and emulsified in a reaction vessel, and slowly mixed for 10 minutes. Furthermore, an emulsion was obtained by adding a solution in which 0.15 part of ammonium persulfate was dissolved in 7 parts of ion-exchanged water and performing nitrogen substitution. Thereafter, while stirring, the emulsion is heated until the temperature of the emulsion reaches 70 ° C., and in this state, the emulsion polymerization is continued for 6 hours. The resin fine particles have a volume average particle diameter of 190 nm, a glass transition temperature of 55 ° C., and weight. An anionic resin fine particle dispersion 2 having an average molecular weight of 830000 was obtained.

  Cyan pigment C.I. I. Pigment Blue 15: 3 (Dainippon Ink Chemical Co., Ltd.) 50 parts, anionic surfactant Neogen R (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts and ion-exchanged water 200 parts were mixed together, and the homogenizer Ultra Turrax ( (Prepared by IKA) for 10 minutes, and further dispersed by a sand mill for 2 hours to obtain a colorant dispersion having a volume average particle size of 140 nm and a solid content of 21.5% by weight.

  50 parts of bisphenol compound 1, 3 parts of anionic surfactant Neogen R (Daiichi Kogyo Seiyaku Co., Ltd.) and 200 parts of ion-exchanged water are mixed, and pre-dispersed for 10 minutes with ultra turrax (manufactured by IKA) as a homogenizer. Further, by dispersing for 2 hours with a sand mill, a bisphenol compound dispersion having a solid content of 21.1% was obtained.

  After mixing 7.0 parts of paraffin wax HNPO190 (manufactured by Nippon Seiwa Co., Ltd.) having a melting point of 85 ° C., 1.1 parts of anionic surfactant Neogen R (made by Daiichi Kogyo Seiyaku Co., Ltd.) and 18 parts of ion-exchanged water, A release agent dispersion having a volume average particle size of 250 nm was obtained by heating to 95 ° C. and dispersing with a high-pressure homogenizer.

  0.18 parts of polyaluminum chloride PAC (manufactured by Asada Chemical Co., Ltd.) and 1.8 parts of 0.1 wt% nitric acid aqueous solution were mixed and stirred in a bottle to obtain an aqueous flocculant solution.

  For the following stirring and dispersion, an in-line stirring / dispersing apparatus was used. This apparatus is composed of a stirring tank, a loop pipe that circulates from the bottom of the stirring tank to the top of the stirring tank, and a disperser Cavitron CD1010 (manufactured by Taiheiyo Kikai Co., Ltd.) inserted in the middle of the loop pipe. The tank is provided with a jacket capable of cooling the stirring tank with cooling water as a cooling means.

  Using an in-line type dispersion / stirring device, 8.35 parts of resin fine particle dispersion 1, 5.5 parts of resin fine particle dispersion 2, 2.1 parts of colorant dispersion, 0.5 parts of bisphenol compound dispersion Mix well from a mixture of 2.8 parts of release agent dispersion and 43 parts of ion-exchanged water in a stirring tank, and then mix from the bottom valve of the stirring tank while gradually adding 1.5 parts of an aqueous flocculant solution. The liquid was introduced into the disperser and dispersed at a rotor peripheral speed (outermost peripheral speed) of 36 m / second, and the mixed liquid that passed through the disperser was circulated again to the upper part of the stirring tank for 10 minutes. When the agglomerated particles contained in the mixed solution after the stirring and dispersion were measured with a Coulter counter Multimizer II (manufactured by Coulter Inc.), the volume average particle diameter was 3.1 μm. In addition, the temperature of the liquid mixture at this time was 32 degreeC.

  Next, this liquid mixture was heated to 52 degreeC with the stirring tank with a heating jacket, and was hold | maintained for 90 minutes. When the mixed solution after the heat treatment was measured with a Coulter counter, aggregated particles having a volume average particle diameter of 5.5 μm were confirmed. When 4.3 parts of the resin fine particle dispersion 1 was gently added to this mixed liquid and kept for 1 hour, aggregated particles having a volume average particle diameter of 6.0 μm were confirmed.

Next, 1.5 parts of a 4% by weight aqueous sodium hydroxide solution was added to the mixture, heated to 95 ° C., and held for 4 hours to fuse the aggregated particles. Then, after cooling and filtering through a nylon mesh having a pore size of 20 μm, and further filtering through a filter cloth having a pore size of 3 μm, the filtrate on the filter cloth is sufficiently washed with ion exchange water, and the filtrate is vacuum dried. And dried to obtain toner base particles. The toner base particles had a volume average particle size of 6.0 μm, a number average particle size of 5.4 μm, and an average circularity of 0.968. Next, 100 parts of toner base particles, 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide were mixed using a Henschel mixer to obtain a toner.
(Comparative Example 1)
A toner was prepared in the same manner as in Reference Example 1 except that bisphenol compound 1 was not added.
(Comparative Example 2)
A toner was prepared in the same manner as in Reference Example 2 except that bisphenol compound 1 was not added.
(Comparative Example 3)
A toner was prepared in the same manner as in Reference Example 3, except that zinc salicylate E-304 (manufactured by Orient Chemical Co., Ltd.) was used instead of bisphenol compound 1.
(Comparative Example 4)
A toner was prepared in the same manner as in Reference Example 4 except that zinc salicylate E-304 (manufactured by Orient Chemical Co., Ltd.) was used instead of bisphenol compound 1.
(Comparative Example 5)
Chemical structural formula instead of bisphenol compound 1

で示されるビスフェノール化合物５を用いた以外は、参考例１と同様にトナーを作製した。
（比較例６）
ビスフェノール化合物１の代わりに、化学構造式

A toner was prepared in the same manner as in Reference Example 1 except that the bisphenol compound 5 shown in FIG.
(Comparative Example 6)
Chemical structural formula instead of bisphenol compound 1

で示されるビスフェノール化合物５を用いた以外は、参考例１と同様にトナーを作製した。
（比較例７）
ビスフェノール化合物分散液を加えずに、加熱温度及び時間を適宜調節してトナー母粒子を得た以外は、参考例８と同様に、トナーを作製した。
（分子量の測定）
樹脂の分子量は、ＧＰＣ（Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ）を用いて求めた。具体的には、ＨＬＣ−８２２０ＧＰＣ（東ソー社製）を用い、カラムＴＳＫｇｅｌ ＳｕｐｅｒＨＺＭ−Ｍ ｘ ３の温度を４０℃、テトラヒドロフランの流速を０．３５ｍｌ／分に設定して、濃度０．０５〜０．６％の試料を０．０１ｍｌ注入することにより、測定した。

A toner was prepared in the same manner as in Reference Example 1 except that the bisphenol compound 5 shown in FIG.
(Comparative Example 7)
A toner was prepared in the same manner as in Reference Example 8 except that toner base particles were obtained by appropriately adjusting the heating temperature and time without adding the bisphenol compound dispersion.
(Measurement of molecular weight)
The molecular weight of the resin was determined using GPC (Gel Permeation Chromatography). Specifically, HLC-8220GPC (manufactured by Tosoh Corporation) was used, the temperature of the column TSKgel SuperHZM-M x 3 was set to 40 ° C., and the flow rate of tetrahydrofuran was set to 0.35 ml / min. Measurements were made by injecting 0.01 ml of a 6% sample.

The weight average molecular weight was calculated from the molecular weight distribution of the resin measured under the above conditions, using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample. As the monodisperse polystyrene standard sample, 10 samples in the range of 5.8 × 100 to 7.5 × 1000000 were used.
(Evaluation method and evaluation results)
The toner was placed in a black toner cartridge of LP-1500C (manufactured by Epson Corporation), and scumming was observed at the initial stage and after 800 sheets of blank paper. Note that the lower the background stain, the better the chargeability of the toner.

  Judgment was made with ◯ when the soil was scarcely seen, slightly seen but Δ when the level was not anxious, and x when it was noticeable.

  The heat resistant storage stability was evaluated as follows. 20 g of toner was put in a 20 ml glass bottle and allowed to stand in a constant temperature bath at 55 ° C. for 24 hours, and then the toner was cooled to 24 ° C. and subjected to a penetration test (JIS K2235-1991). A toner having a high penetration is superior in heat-resistant storage stability. When the penetration is 15 mm or less, there is a high possibility that a problem in use will occur.

  The heat-resistant storage stability was judged as ◯ when the penetration was 20 mm or more, Δ when the penetration was 15 mm or more and less than 20 mm, and × when the penetration was less than 15 mm. The results are shown in Table 1.

これより、実施例５、参考例１〜４、６〜８のトナーは、帯電性が良好で耐熱保存性に優れることがわかる。

From this, it can be seen that the toners of Example 5, Reference Examples 1 to 4 and 6 to 8 have good chargeability and excellent heat-resistant storage stability.

It is a figure which shows an example of the image forming apparatus used by this invention. FIG. 2 is a schematic diagram of a developing device of the image forming apparatus in FIG. 1.

Explanation of symbols

1Y, 1M, 1C, 1K Developing device 101 Fixing device 102 Photoconductor belt 104 Exposure device 105 Charging device 106 Paper feed cassette 106a Recording medium 107 Transfer drum 1 Toner storage chamber 2 Toner 3 Conveying blade 4 Supply roll 5 Developing roll 6 Regulating blade

Claims (6)

Chemical formula

A toner comprising a compound represented by the formula: Chemical formula

A step of preparing a first liquid by dissolving or dispersing a material containing a compound represented by the above, a binder resin and a colorant in an organic solvent;
A method for producing a toner, comprising a step of dispersing the first liquid in an aqueous solvent. Chemical formula

A step of preparing a first liquid by dissolving or dispersing in a monomer a material containing a compound represented by:
Emulsifying the first liquid in an aqueous solvent to prepare a second liquid;
Polymerizing the monomer contained in the second liquid to produce a dispersion;
A method for producing a toner, comprising a step of agglomerating the dispersion with a dispersion containing a dispersion of a colorant and fusing the dispersion. Chemical formula

A step of producing a dispersion by dispersing a material containing a compound represented by the formula:
A method for producing a toner, comprising a step of aggregating and fusing the dispersion. Chemical formula

A step of preparing a first liquid by dissolving or dispersing a material containing a compound and a colorant represented by:
Dispersing the first liquid in an aqueous solvent to prepare a second liquid;
A method for producing a toner, comprising a step of polymerizing the monomer contained in the second liquid.   An image forming method comprising forming an image using the toner according to claim 1.

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